TW461929B

TW461929B - Product and method for improving the strength of lignocellulosic material under humid conditions

Info

Publication number: TW461929B
Application number: TW088119766A
Authority: TW
Inventors: Blair Alex Owens; Dimitris Ioannis Collias; Andrew Julian Wnuk
Original assignee: Paper Technology Foundation In
Priority date: 1998-11-12
Filing date: 1999-11-11
Publication date: 2001-11-01
Also published as: EP1131485A1; US6114471A; AU1345200A; WO2000029670A1

Abstract

The strength of lignocellulosic materials is improved by treating them with water-soluble strengthening agents containing sulfonic units, and rendering these agents water-insoluble by reacting them with compounds containing azetidinium rings. Thus, a substantial reduction or elimination of the bleeding of said strengthening agents from the lignocellulosic materials when touched with wet hands or contacted under humid conditions is achieved.

Description

461929 五、發明說明（1 ) 發明領域本發明係有關於改良木質纖維素材料之強度之產物及方法。發明背景木、：纖維素材料’如紙及硬紙板，可用各種強化劑之溶液或刀散屣加以處理（例如，塗覆、浸潰等）而強化。這些溶液或分散液之實例爲木質磺酸鹽之水溶液。木質磺酸鹽係木質續酸之金屬或按鹽。木質續酸鹽不是亞硫酸鹽製梁法心副產物’便是其他木質衍生物之續酸化產物。木質衍生物包括，但不限於，牛皮紙木質、有機溶膠木質、化學改質木質衍生物，及彼等之混合物。然而，使用這些強化劑二重大缺點爲在與濕手接觸時，彼等會有木質纖維素材料渗出。這將看起來不美觀，而且疗祿不堪。另一重大門題是，這些強化劑在高濕度下之強度保留較正常濕度(例如，50% RH)下爲低。再者，此—問題預期是由彼等對水及水氣之高親和力所引起。經濟部智ff費合作社印製一種提高木質纖維素材料在高濕度情況下之強度的普通方法爲在材科中添加额外纖維。然而，此一方法同樣並血成本效益，因爲多了額外纖維/材料之成分。另一種消除或減少水溶性強化劑滲出之方法爲以犧或聚合物膜塗覆經處理《木質纖維素材料。然而’此一方法並非有效的解決万法’因爲二次塗覆材料採購、處理及使用都很昂貴，而且在正常狀況下都不能再製成漿。還有另一種消除或減少水溶性強化劑滲出之方法是藉交本紙張尺度適用尹國國家標準（CNS)A4規格（21〇x297公羞） 461929 A7 B7 五、發明說明（2 聯使其變成不溶性。在木質磺酸鹽之情況時，文獻已報告的交聯反應包括以下：在高溫下與強礦物酸之縮合反應 (經由SO,單元），與過氧化氫及觸媒之氧化偶合反應（經由0H-基），與雙_重氮鹽之反應（經由α _位置至〇H.基），與雙官能醯基氯之反應（經由〇Η-基），與氰尿醯氣之反應 (經OH—基），與曱醛之反應（經由Ch2基），與糠醛之反應 (經由α _位置至0H-基）及與表氯醇之反應（經由〇H基）。，二而以上反應/方法都包括各種加工處理問題，如成本，低pH，長反應時間，嚴苛條件（例如，溫度），健康危害等等。所人缺的疋一種價廉產物，及一種改良經處理木質纖維素材料在潮濕情況下之強度之簡單，低廉又快速方法，該万法係使水溶性強化劑反應，以便在與濕手接觸或在潮濕狀況下被接觸時，使水溶性強化劑自材料之滲出實少或消除。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製發明概述本發明係有關於改良木質纖維素材料強度之產物及方法。強度改艮係藉以具有至少一個磺酸單元之水溶性強化劑處理木質纖維素㈣並藉㈣财fim具至少K 4環之化合物反應而使該強化劑變成水不溶性而達成。此將造成在與濕手接觸或在潮濕情況下被接觸時，原本水溶性之強化劑自木質纖維素材料滲出之問題實質減少或消除。登明之詳細激日已知，木質纖維素材料之強度（例如，紙，襯紙板，瓦拇461929 V. Description of the invention (1) Field of the invention The present invention relates to products and methods for improving the strength of lignocellulosic materials. BACKGROUND OF THE INVENTION Wood, cellulosic materials, such as paper and cardboard, can be strengthened by treating (e.g., coating, impregnating, etc.) with a variety of strengthening agent solutions or a knife. Examples of these solutions or dispersions are aqueous solutions of lignosulfonate. Lignosulphonate is a metal or salt of lignosulfonic acid. Lignosalts are either the byproducts of the sulfite beam method, or the acidification products of other wood derivatives. Wood derivatives include, but are not limited to, kraft paper wood, organosol wood, chemically modified wood derivatives, and mixtures thereof. However, the two major disadvantages of using these fortifiers are that they will ooze out of lignocellulosic materials when in contact with wet hands. This will look unsightly and unbearable. Another major issue is that these fortifiers have lower strength retention under high humidity than normal humidity (e.g., 50% RH). Furthermore, this—problem is expected to be caused by their high affinity for water and water vapor. Printed by the Intellectual Property Cooperative of the Ministry of Economic Affairs A common method to increase the strength of lignocellulosic materials under high humidity conditions is to add additional fiber to the material family. However, this method is also cost-effective because of the extra fiber / material component. Another way to eliminate or reduce the exudation of water-soluble enhancers is to coat the treated lignocellulosic material with a sacrificial or polymer film. However, this method is not an effective solution because secondary coating materials are expensive to purchase, handle, and use, and cannot be made into pulp under normal conditions. There is another way to eliminate or reduce the exudation of water-soluble fortifiers by submitting this paper to the national standard (CNS) A4 specification (21 × 297). 461929 A7 B7 V. Description of the invention Insolubility. In the case of lignosulfonate, the cross-linking reactions reported in the literature include the following: condensation reaction with strong mineral acids at high temperature (via SO, unit), oxidative coupling reaction with hydrogen peroxide and catalyst ( Via 0H-group), reaction with di-diazonium salt (via α-position to 0H. Group), reaction with bifunctional fluorenyl chloride (via OH-group), reaction with cyanuric acid (by Via OH-group), reaction with formaldehyde (via Ch2 group), reaction with furfural (via α-position to 0H- group), and reaction with epichlorohydrin (via OH group). Two or more reactions / Methods include various processing issues such as cost, low pH, long reaction time, harsh conditions (eg, temperature), health hazards, etc. What people lack is a cheap product and an improved treated wood fiber The strength of plain materials under wet conditions is simple, Inexpensive and fast method, this method makes the water-soluble fortifier react so as to make the water-soluble fortifier seep out from the material when it comes into contact with wet hands or under wet conditions. (Please read the back first Please note this page, please fill out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative Summary of the Invention The present invention relates to products and methods for improving the strength of lignocellulosic materials. The strengthening agent treats the lignocellulose and makes the strengthening agent become water-insoluble by reacting the compound with at least K 4 ring. This will cause the water-soluble agent to contact with wet hands or be exposed to moisture. The problem of exudation of lignocellulosic materials from lignocellulosic materials is substantially reduced or eliminated. As detailed in detail, the strength of lignocellulosic materials is known (for example, paper, linerboard, tile thumb).

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I I- I n · 461929 經濟部智慧財產局員工消費合作社印製 A7 ___ _B7 五、發明說明（3) 紙板，硬紙板等等）可用強化劑（例如，矽酸鈉，澱粉，羧基甲基纖維素.C，木聚糖等等）之各種水溶液處理而改良。很遺憾地，這些水溶性強化劑在與濕手接觸或在潮濕情沉下被接觸時，都會自材料滲出。木質磺酸鹽是也可用於強化木質纖維素材料之水溶性強化劑。木質磺酸鹽含有磺酸單元（HSCV;亦稱爲亞硫酸氫單元）及磺fe鹽單元（SOs2-;亦稱爲亞硫酸鹽單元），且爲本揭示之用，”磺酸”一詞將用於涵蓋"磺酸"與，，磺酸鹽” 單儿。預期木質磺酸鹽係經由包封及/或穿透增強木質纖維素材料之纖維及/或纖維黏合而使其強化。木質磺酸鹽是可以使用的許多可能木質衍生物的實例。木質衍生物包括，但不限於，牛皮紙木質，有機溶膠木質，化學改質木 λ衍生物（其中保留親核績酸單元）及其混合物。出人意外地發現，木質磺酸鈣水溶液（LIGN〇SITE 5〇_含 40%木質磺酸鈣及1〇%惰性固體；可自司 ’ Atlanta，GA購得）與KYMENE水溶液（KYMENE 557LX-含 12.5% 固體；可自 Hercules公司，Wilmingt〇n，DE購得）起/昆&時產生實際立即之反應而產生沈澱物。此沈殿物具水不溶性性質。這一混合係一簡單，成本低又快速之過紅’可在周圍條件下進行，不需使用複雜的設備。也出人思外地發現’木質續酸鈉水溶液（LIGN〇SITE 458 ;可自 Georgia-Pacific 公司購得）及木質磺酸銨（lign〇SItE 174〇) 與 KYMENE 水溶液（kymeNE 557LX-含 12.5% 固體；I I- I · 461929 Printed by A7 _ _B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3) Cardboard, cardboard, etc.) Strengthening agents (eg, sodium silicate, starch, carboxymethyl fiber) V.C., xylan, etc.) are improved by treatment with various aqueous solutions. Unfortunately, these water-soluble fortifiers exudate from the material when they come in contact with wet hands or when they are exposed to moisture. Lignosulfonate is a water-soluble enhancer that can also be used to strengthen lignocellulosic materials. Lignosulfonate contains a sulfonic acid unit (HSCV; also known as a hydrogen sulfite unit) and a sulfonic acid salt unit (SOs2-; also known as a sulfite unit), and for the purpose of this disclosure, the term "sulfonic acid" Will be used to cover " sulfonic acids " and, sulfonates ". Lignosulfonates are expected to be strengthened by encapsulating and / or penetrating the fibers and / or fiber binding of the lignocellulosic material to strengthen it Lignosulphonate is an example of many possible wood derivatives that can be used. Wood derivatives include, but are not limited to, kraft paper wood, organosol wood, chemically modified wood lambda derivatives (where nucleophilic acid units are retained) and Surprisingly, it was found that an aqueous solution of calcium lignosulfonate (LIGNOSITE 50% contains 40% calcium lignosulfonate and 10% inert solids; available from the company 'Atlanta, GA) and an aqueous solution of KYMENE (KYMENE 557LX- containing 12.5% solids; available from Hercules, Wilmington, DE) / Kun & produce an immediate reaction to produce a precipitate. This Shen Dian material has water-insoluble properties. This mixing system is simple , Low cost and fast Red 'can be carried out under ambient conditions without the need for complicated equipment. Surprisingly, it has also found' aqueous sodium lignosulphate solution (LIGNOSITE 458; available from Georgia-Pacific) and ammonium lignosulfonate (lign 〇SItE 174〇) and KYMENE aqueous solution (kymeNE 557LX- containing 12.5% solids;

Hercules公司出品）分別一起混合時產生實際立即之反應而 -6- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------------1訂---------1 (請先閱讀背面之注意事項再填寫本頁) 4 6 1929 A7 B7 五、發明說明（4) 產生沉澱物。 K YMENE是一種聚胺聚醯胺表氫醇{亦稱爲a)聚氨基醯胺表氯醇’ b)聚（氨基酿胺）表氯醇，.幻氨基聚醯胺表氯醇，d)聚醯胺表氯醇，或e) PAE}化合物，其用作爲紙張應用之濕強劑。KYMENE之製備在Keim之美國專利 2,926，116.號（1960年2月23曰頒予）及5^111之美國專利 3,332,901號（1967年7月2 5曰頒予）中已有詳細説明。雖然已知，KYMENE對本身有很強的親和力（用其主要會與本身交聯）及對纖維素或CMC(經由纖維素之羧基）有些微親和力，但未曾揭示或發現KYMENE對木質磺酸鹽有很強的親和力。可用聚醯胺-聚胺-表氯醇化合物之—商業來源係Hercules 公司（Wilmington，Delaware)，其推出之此種化合物，商品名爲KYMENE 557H，如美國專利2,926,116號所指。其他 KYMENE產品具有延伸代號557LX，SLX，SLX2或ULX。可用聚醯胺-聚胺-表氯醇化合物之另一商業來源爲Henkel公司’其推出之此種化合物，商標爲Fibrabond，如美國專利 5,239,047號所指。含吖啶環之另一可能可用化合物（目前市面上未出售）已説明於美國專利5,510,〇〇4號（讓渡與Produced by Hercules company) when they are mixed together, they produce an actual and immediate response. -6- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------- ---- 1 Order --------- 1 (Please read the notes on the back before filling this page) 4 6 1929 A7 B7 V. Description of the invention (4) A precipitate is generated. K YMENE is a polyamine polyamidoepihydrin {also known as a) polyaminoamidoepichlorohydrin 'b) poly (aminoaminoamine) epichlorohydrin, p-aminopolyamidoepichlorohydrin, d) Polyamidoepichlorohydrin, or e) PAE} compounds, are used as wet strength agents for paper applications. The preparation of KYMENE is described in detail in US Patent No. 2,926,116. (Issued February 23, 1960) by Keim and US Patent No. 3,332,901 (issued July 25, 1967) by 5 ^ 111. Although it is known that KYMENE has a strong affinity for itself (it mainly crosslinks with itself) and a slight affinity for cellulose or CMC (via the carboxyl group of cellulose), KYMENE has not been revealed or found to be lignosulfonate Have a strong affinity. Commercially available polyamido-polyamine-epichlorohydrin compounds are commercially available from Hercules (Wilmington, Delaware). Such compounds are available under the trade name KYMENE 557H, as indicated in U.S. Patent No. 2,926,116. Other KYMENE products have extensions 557LX, SLX, SLX2 or ULX. Another commercial source of polyamido-polyamine-epichlorohydrin compounds is Henkel Corporation ' which launches such compounds under the trademark Fibrabond, as indicated in U.S. Patent No. 5,239,047. Another potentially useful compound containing an acridine ring (not currently on the market) is described in U.S. Patent No. 5,510,004 (assigned to

Hercules公司；1996年4月23日頒予）。不願受理論約束，今假設交聯係在木質磺酸鹽之高度親核磺酸或磺酸鹽單元與KYMENE之吖啶環（-N+-(CH2)2-CH-OH) 間進行。再者，咸信3 _ D分子結構，活性單元間隔及數量密度及位阻效應都在決定交聯聯合之強度上扮演重要負 -7- (請先閱讀背面之注意事項再填寫本頁) ---- 訂---------錄，經濟部智慧財產局員工消費合作社印製太紙張疋唐 i南用 Φ 圃 /^χτ^ν - _ ..... 干 ί I i ί i 211 (\ 格愛公 97 461929 A7 ___B7_ 五、發明說明（5) 色。以上假設業經各種系列之試驗。第一系列係用各種木質磺酸鹽溶液與KYMENE試驗以確定那一種之反應與 LIGNOSITE 50 相似。在 Westvace 公司（New York, NY)， Lignotech公司（Bridgewater, NH)及Georgia-Pacific公司提供的3 2種木質磺酸鹽溶液中，只有9種（Westvacos之REAX 83A，Lignotech 之 WANIN S，Lignotech 之 NORLIG G， Lignotech 之 MARASPERSE N-22，Lignotech 之 WELLTEX 200，Lignotech 之 WELLTEX 300，Lignotech 之 WELLTEX 300F，Georgia-Pacific 之 LIGNOSITE 1740，及 Georgia-pacific 之 LIGNOSITE 458)形成類似於LIGNOSITE 50所形成之沉澱物。在另一系列之試驗中，牛皮紙木質（Indulin AT Westvaco公司出品），其具經基但無確酸/績酸鹽單元，不會與KYMENE形成沉澱物。在又一系列之試驗中，具磺酸而無羥基單元之聚苯乙烯磺酸鹽（Aldrich公司出品）與 KYMENE混合，即產生沉澱物。然而，聚磺酸乙烯酯 (Aldrich公司出品）與KYMENE混合時不會形成沉澱物。以上全部試驗都指向一事實，即化合物中有磺酸/磺酸鹽單元之存在是此化合物與KYMENE反應形成沉澱物之必要但非充分條件。因此，除磺酸/磺酸鹽單元外，以上試驗也指出，3 - D分子結構，活性單元間隔及數量密度，及位阻效應都在沉澱物之有無及強度上扮演決定性之角色。另一方面，有關反應機制之KYMENE中吖啶環之重要性曾試圖由聚氯化二晞丙基二甲基銨（亦即，第四胺）（具分 -8 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ------.—訂---------姨，經濟部智慧財產局員工消費合作社印製 461929 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6 ) 于重约ιυυ,υυυ玍ζυυ,υυυ)興,_ __ , ’…工物爲二種聚合化合物之稠化漿體，不像木質續酸鹽與 ΚΥΜΕΝΕ間之沉濺物。再者，其他聚合胺，如聚乙晞亞胺 (ΡΕΙ)與木質磺酸鹽反應也產生類似的水溶性稠化漿體。在另一系列之試驗中，發現木質磺酸鹽與ΚΥΜΕΝΕ間之沉澱物只在某一 pH範圍内才會保持水不溶性。更明確言之，已發現某些鹼性條件，其可視反應之化合物而定，會使沉澱物溶解。例如，木質磺酸鈣（LIGN〇SITE 5〇 ; Georgia-Pacific公司出品）與 KYMENE 557LX(Hercules公司出品）反應形成之沉澱物會在水溶液中溶解，若p H爲約Η 或更高。此交聯反應及處理可在材料製造過程之任何階段，包括漿粕階段，造紙過程之濕端（例如，流料箱或形成段或壓縮段）及乾端（例如，烘乾段或壓漿）施加於木質料，或甚至將已加工處理之材料（例如，襯紙板及圖紙)洪乾）並形成最終產物（例如，瓦楞板）。一般而女，有—種方法可用以形成沉澱物並將其施用於木質纖維素材料。種第—種方法是沉澱物在木f纖維切科巾形成 =二：第二種/法是沉澱物先形成，再施加於木質纖維素材科。就地法之一種變化是具貞單元之水溶性強化劑先施加料質纖維素二個=核續酸加具有至少一個,丫啶環之化合物。就：、，其次再施具有至少，唉環之化合物先施質：另-變化是其次再施加具有至少—個親㈣酸單元之2維素材料，尺’谷性強化劑。Hercules; awarded April 23, 1996). Without wishing to be bound by theory, it is assumed that the cross-linking takes place between the highly nucleophilic sulfonic acid or sulfonate unit of lignosulfonate and the acridine ring (-N +-(CH2) 2-CH-OH) of KYMENE. Furthermore, the molecular structure, active unit spacing, number density, and steric hindrance effect of Xianxin 3_D all play an important negative role in determining the strength of the cross-linking association. -7- (Please read the precautions on the back before filling this page)- --- Order --------- Records, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed on paper, used in the south and ΦΦ / ^ χτ ^ ν-_ ..... ί i 211 (\ 格爱公 97 461929 A7 ___B7_ 5. Description of the invention (5) color. The above assumptions have been tested in various series. The first series uses various lignosulfonate solutions and KYMENE tests to determine which kind of reaction and LIGNOSITE 50 is similar. Of the 32 lignosulfonate solutions provided by Westvace (New York, NY), Lignotech (Bridgewater, NH) and Georgia-Pacific, only 9 (REAX 83A from Westvacos, and WAIN from Lignotech) S, Norglig G of Lignotech, MARASPERSE N-22 of Lignotech, WELLTEX 200 of Lignotech, WELLTEX 300 of Lignotech, WELLTEX 300F of Lignotech, LIGNOSITE 1740 of Georgia-Pacific, and LIGNOSITE 458 of Georgia-pacific) form similar to LIGNOS Precipitation formed by ITE 50. In another series of tests, kraft paper wood (manufactured by Indulin AT Westvaco), which has a base but does not have acid / phosphate units, will not form a precipitate with KYMENE. In a series of experiments, a polystyrene sulfonate (manufactured by Aldrich) with sulfonic acid and no hydroxyl unit was mixed with KYMENE, and a precipitate was produced. However, when polyvinyl sulfonate (manufactured by Aldrich) was mixed with KYMENE No precipitate will be formed. All of the above tests point to the fact that the presence of sulfonic acid / sulfonate units in the compound is a necessary but not sufficient condition for the compound to react with KYMENE to form a precipitate. Therefore, except for sulfonic acid / sulfonic acid In addition to the acid salt unit, the above experiments also pointed out that 3-D molecular structure, active unit spacing and number density, and steric effects all play a decisive role in the presence and intensity of the precipitate. On the other hand, KYMENE related to the reaction mechanism The importance of the acridine ring has been attempted by poly (dimethypropylpropyldimethylammonium chloride) (that is, the fourth amine) (minus -8-this paper size applies to Chinese National Standard (CNS) A4 Grid (210 X 297 mm) (Please read the precautions on the back before filling out this page) ------.-- Order ------------ Aunt, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 461929 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the Invention (6) Yu Zhong, υυυυυ 玍 ζυυ, υυυ) Xing, _ __, '... The working substance is a thickened slurry of two polymer compounds Body, unlike the splatter between lignosalt and κΜΕΝΕ. Furthermore, other polymeric amines, such as polyethyleneimine (PEI), react with lignosulfonate to produce similar water-soluble thickened slurries. In another series of experiments, it was found that the precipitate between the lignosulfonate and κΜΕΝΕ remains water-insoluble only within a certain pH range. More specifically, it has been found that certain basic conditions, depending on the compounds reacted, can dissolve the precipitate. For example, the precipitate formed by the reaction of calcium lignosulfonate (LIGNOSITE 50; manufactured by Georgia-Pacific) and KYMENE 557LX (produced by Hercules) will dissolve in an aqueous solution, if pH is about Η or higher. This cross-linking reaction and treatment can be at any stage of the material manufacturing process, including the pulp stage, the wet end of the papermaking process (for example, headbox or forming section or compression section) and the dry end (for example, drying section or press section). ) Applied to wood, or even flood-processed materials (eg, linerboards and drawings) and formed into final products (eg, corrugated boards). Generally, there are methods for forming a precipitate and applying it to a lignocellulosic material. Species The first method is to form a precipitate in the wood fiber cutting branch = two: the second method is to first form the precipitate and then apply it to the wood fiber material family. One variation of the in-situ method is that a water-soluble enhancer with a chastity unit is first applied with two cellulose materials = nuclear acid and a compound having at least one acridine ring. For: ,, secondly, the compound with at least the fluorene ring is applied first: another-the change is that the second-dimensional element with at least one philophilic acid unit is applied next, the ruler's grain enhancer.

本紙張尺度適用中國國家標準(CNS)A4m~^ 297公釐） 461929 A7This paper size is applicable to Chinese National Standard (CNS) A4m ~ ^ 297 mm) 461929 A7

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461929 A7 Β7 8 五、發明說明（類似於木質磺酸鹽與KYMENE溶液之混合物所得沉澱物。同樣地，KYMENE可以固體形式（例如，粉末）或液體形式 (例如，水溶液或水分散液，或水與有機溶劑之混合物）使用。一般而言，強化劑溶液或分散液之溶劑或分散劑可含或不含水，亦即，可為完全是水，或完全是有機，或其可為水與有機溶劑之混合物。再者，強化劑可為純粹型或與其他惰性或活性劑之混合物。經木質碟酸鹽-KYMENE處理之紙張，其木質磺酸鹽滲出之實質減少或消除，以及經木質磺酸鹽_ κγΜΕΝΕ處理461929 A7 B7 8 V. Description of the invention (similar to the precipitate obtained from a mixture of lignosulfonate and KYMENE solution. Similarly, KYMENE can be in solid form (eg, powder) or liquid form (eg, aqueous solution or aqueous dispersion, or water With organic solvents). In general, the solvent or dispersant of the enhancer solution or dispersion may or may not contain water, that is, it may be completely water, or it may be completely organic, or it may be water and organic Mixture of solvents. In addition, the strengthening agent may be pure or mixed with other inert or active agents. Paper treated with Kymene-KYMENE has substantially reduced or eliminated leachate sulfonate, and lignosulfonate _ ΚγΜΕΝΕ treatment

之紙張’其在1¾濕度下之鬲強度保留，將顯示於以下三個實例中D 實例1 將紙樣本浸沒於水中若干天，檢驗滲出之消除。製備二組樣本。第一組樣本係使用35#襯紙板（亦即，3 5磅/〗〇〇〇平方叹；35 lb/msf ; 170 g/m2或no克 /平方米；Ge〇rgia_Pacific 公司之產品（USP70)浸入木質磺酸鈣之水溶液（Ge〇rgia_ Pacific公司的LIGNOSITE 50 ; 40%木質磺酸鹽固體及ι〇〇/0惰性固體）中1分鐘製成。第二組樣本係使用35#襯紙板先浸入木質續酸鹽之水溶液中1分鐘，然後擦掉過量水溶液，再澱入5.0% KYMENE 557LX(Hercules公司出品）之水溶液中1 0秒。二組樣本都夾在二個加熱之壓板間於l77〇C下烘乾1 0秒。然後，二組樣本都浸沒於室溫水中至少三天。經木質磺酸鹽處理之樣本四周的水變成深褐色，顯示 -11 - (請先閱讀背面之注意事項再填寫本頁) !丨丨丨訂.!--丨1線經濟部智慧財產局員工消費合作社印製 w / \ - ί r i ·'· Μ 公 9/ Ζ X 3 461929 A7 B7 五、發明說明（9) 木質磺酸鹽自樣本滲出該量。然而經木質磺酸鹽_ KYMENE處理之樣本四周的水則保持透明無色，顯示並無木質磺酸鹽自樣本滲出。實例2 在一設計用以測定經木質磺酸鹽-KYMENE處理之襯紙板在80% RH下之耐濕性之試驗中，如實例1先以木質續酸鹽約處理’再以KYMENE處理35#觀紙板（Georgia-Pacific公司之產品USP70)。此經木質磺酸鹽_ KYMENE處理之襯紙板之強度’然後再藉進行環壓碎試驗（Ring Crush te.:st， RCT ; TAPPI標準T822-om93)加以測試，其中，經木質磺酸鹽，KYMENE處理之襯紙板具66.1 ±3.9 lbf/6im之値。僅以木質磺酸鈣處理之相同襯紙板（如實例1 )之RCT値爲61.7 ± 3.7 lbf/6im。因此，結論是，當襯紙板以木質績酸鹽及 KYMENE處理時，經木質磺酸鹽_ ΚΥΜΕΝΕ處理之襯紙板在80% RH下之強度較經木質磺酸鹽處理之櫬紙板增加 7 % (在99%置信水準下統計上顯著）。實例3 在設計用以測定處理對箱壓縮之影響之另一系列試驗中，製作各種RSC-型（正常槽缝容器）瓦楞箱（c_溝槽構型），長度 28 cm(ll in.)，寬度21.6 cm(8.5 in.)，高度20.3 cm(8 in.) 及摺翼寬5 cm(2 in.)。製作三系列箱子。第一系列係以未處理襯紙板及介質（對照箱子）製作。櫬紙板爲35#(Georgia-Pacific公司之產品 USP70)及介質爲 26#(127 gsm ; Georgia-Pacific公司出品）。另二個系列係以經處理的35#襯紙板及 Ί2- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） (請先閲讀背面之注意事項再填寫本頁) '-1 I 丨訂，---------線，經濟部智慧財產局員工消費合作社印製經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（1〇 ) 未處理的26#介質製造。對照瓦楞紙板之單位重量爲573 克。在第二系列中，襯紙板係以木質磺酸鹽水溶液 (LIGNOSITE 50 ; Georgia-Pacific公司出品；40%木質磺酸鹽固形物及10%惰性固形物）使用MIPLY試驗規模加壓飽和機（位於 Vits Maschinenbau 公司，Langenfeld，Germany)處理。所達成的加入量爲37%，瓦楞紙板之單位重量爲683 gsm(亦即，較未處理瓦楞紙重19%)。最後，在第三系列中，襯紙板係以木質續酸#5 (類似於第二系列；3 5 %加入量）處理，再以KYMENE 557LX塗覆，該KYMENE 557LX 係自12.5%溶液（Hercules公司出品）以線棒（Mayer)塗覆器 (0.2毫米線直徑：約1 %加入量）施塗。瓦楞紙板之單位重量爲677 gsm (亦即，較未經處理瓦楞紙重18%)。全部系列之箱子均使用Lansmont試驗機（型#76-5 ; Lansing, MI)以十字頭速度 1.27 cm/min(0.5 in/min ; 0.022 cm/s)測試壓縮（根據TAPPI標準T804 om-89)，並報告最大壓縮2.541 cm/1 in 之高岭負荷。未處理（對照）箱在50% RH及80% RH下之高峯負荷分別爲 2711 ±53 N(610± 12 lbf)及 2191 土 80 N(493 ± 18 lbf)。同樣地，以僅經木質磺酸鈣處理之襯紙板製成之箱子之高峯負荷分別爲 3769±213 N(848 ±48 lbf)及2613±53 N(588 ± 12 lbf)。最後，以經木質磺酸鈣及KYMENE處理之襯紙板製成之箱子之高峯負荷分別爲3782 ±440 N(851 ± 99 lbf)及 2884土 129 N(649±29 lbf)。因此，結論是，當以木質磺酸約及KYMENE處理之襯紙板製成瓦楞紙箱時，此經處理之 -13- 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ...衣-------—訂---------β，， 461929The paper's ’strength retention under 1¾ humidity will be shown in the following three examples D Example 1 A paper sample was immersed in water for several days, and the exudation was examined for elimination. Prepare two sets of samples. The first set of samples used 35 # liner board (that is, 35 lbs / 00 square meters; 35 lb / msf; 170 g / m2 or no grams per square meter; products of the company George Pacific (USP70) It was immersed in an aqueous solution of calcium lignosulfonate (LIGNOSITE 50; 40% lignosulfonate solids and ι〇 / 0 inert solids from Georgia Pacific) for 1 minute. The second set of samples was made using 35 # liner paper. Immerse in the aqueous solution of lignosalt for 1 minute, then wipe off the excess aqueous solution, and deposit it in 5.0% KYMENE 557LX (produced by Hercules) for 10 seconds. Both samples were sandwiched between two heated platens at l77. Dry at 10 ° C for 10 seconds. Then, both sets of samples were immersed in room temperature water for at least three days. The water around the samples treated with lignosulfonate turned dark brown, showing -11-(Please read the note on the back first Please fill in this page again !! 丨丨丨 Order.!-丨 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the First-line Ministry of Economic Affairs w / \-ί ri · '· Μ Public 9 / ZE X 3 461929 A7 B7 V. Invention Note (9) The amount of lignosulfonate exuded from the sample. However, it was treated with lignosulfonate _ KYMENE The water around the sample remained transparent and colorless, showing that no lignosulfonate was exuding from the sample. Example 2 A test designed to determine the moisture resistance of a liner board treated with lignosulfonate-KYMENE at 80% RH In Example 1, first treated with lignosulphate and then treated with KYMENE 35 # paperboard (product of Georgia-Pacific USP70). The strength of this paperboard treated with lignosulfonate _ KYMENE was then borrowed The ring crushing test (Ring Crush te.:st, RCT; TAPPI standard T822-om93) was used for testing. Among them, wood sulfonate and KYMENE treated liner had 66.1 ± 3.9 lbf / 6im. Only wood was used. The RCT 値 of the same liner board treated with calcium sulfonate (as in Example 1) was 61.7 ± 3.7 lbf / 6im. Therefore, it was concluded that when the liner board was treated with lignate and KYMENE, it was treated with lignosulfonate_K_ΜΕΝΕ The strength of lined paperboard at 80% RH is 7% higher than that of woodboard treated with lignosulfonate (statistically significant at a 99% confidence level). Example 3 Another design was used to determine the effect of processing on box compression. In a series of experiments, various RSC- (Normal slot container) Corrugated box (c_groove configuration), length 28 cm (ll in.), Width 21.6 cm (8.5 in.), Height 20.3 cm (8 in.) And flap width 5 cm ( 2 in.). Make three series of boxes. The first series was made from untreated linerboard and media (control box).榇 Cardboard is 35 # (product of Georgia-Pacific USP70) and medium is 26 # (127 gsm; produced by Georgia-Pacific). The other two series are treated with 35 # linerboard and Ί2- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 cm) (Please read the precautions on the back before filling this page) '- 1 I 丨 Order, --------- line, printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 V. Description of the invention (1〇) Unprocessed 26 #MEDIA MANUFACTURE. The unit weight of the control corrugated cardboard was 573 grams. In the second series, the liner board is a lignosulfonate aqueous solution (LIGNOSITE 50; produced by Georgia-Pacific; 40% lignosulfonate solids and 10% inert solids) using a MIPLY test scale pressure saturator (located in Vits Maschinenbau, Langenfeld, Germany). The added amount reached was 37%, and the unit weight of the corrugated cardboard was 683 gsm (that is, 19% heavier than untreated corrugated paper). Finally, in the third series, the backing board was treated with woody acid # 5 (similar to the second series; 35% added amount), and then coated with KYMENE 557LX, which is a 12.5% solution (Hercules) (Produced) is applied with a Mayer applicator (0.2 mm wire diameter: about 1% added amount). The unit weight of corrugated paperboard is 677 gsm (that is, 18% heavier than untreated corrugated paper). All series of boxes were tested for compression using a Lansmont testing machine (type # 76-5; Lansing, MI) at a crosshead speed of 1.27 cm / min (0.5 in / min; 0.022 cm / s) (according to the TAPPI standard T804 om-89) , And report a maximum compression of 2.541 cm / 1 in. The peak load of the untreated (control) box at 50% RH and 80% RH was 2711 ± 53 N (610 ± 12 lbf) and 2191 soil 80 N (493 ± 18 lbf). Similarly, the peak loads of boxes made of lined cardboard treated only with calcium lignosulfonate are 3769 ± 213 N (848 ± 48 lbf) and 2613 ± 53 N (588 ± 12 lbf). Finally, the peak loads of boxes made of calcium lignosulfonate and KYMENE-treated linerboard were 3782 ± 440 N (851 ± 99 lbf) and 2884 129 N (649 ± 29 lbf). Therefore, the conclusion is that when a corrugated carton is made from a lignosulfonic acid and KYMENE-treated linerboard, this treated -13- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the precautions on the back before filling in this page) ... clothing ------------ Order --------- β, 461929

經濟部智慧財產局員工消費合作社印製五、發明說明（11 箱子與以僅經木質磺酸鈣處理之襯紙板製成之瓦楞箱相比較，在80% RH下之強度增加1〇〇/〇。經所揭示木質磺酸鹽及κγΜΕΝΕ組合製成之終處理木質纖維素材料也測試再製漿性且在溫和條件下證明可再製成漿，如以下實例所示。實例4 可再製漿性試驗包括三個步驟。第一個步驟爲以粉碎機粉碎紙張樣本，第二步驟爲自粉碎樣本形成手抄紙，及第三步驟爲檢驗及分析所形成的手抄紙。在此可再打漿性研究中共砰估二個樣本：1)對照35#襯紙板（Ge〇rgia_Pacitic公司產品USP70)，2)使用MIPLY’s加壓飽和機以木質磺酸鈣 (Ge0rgia-pacitic公司之 LIGN〇SITE 5〇 ;約 22%加入量）浸潰之35#襯紙板，及3)使ffiMIpLY，s加壓飽和機以木質磺酸鈣 (28彳加入量）漫’貝及使用〇·2 mm直控Mayer棒（約1 %加入量）後塗覆KYMENE 557LX劑（Hercules公司出品）之35#襯紙板。在粉碎步驟中，TAPPI/英國粉碎機（ΤΑρρι t_2〇5)運轉9 分鐘，每分鐘移除125 ml樣本。粉碎機裝配螺旋檔板，附裝3,000 rpm三葉推進器，並裝入去離子水（pH=74)，溫度 38C±6C(l〇〇°F 土 l〇°F)。粉碎步驟所得樣本然後在形成步驟内形成手抄紙。粉碎步驟第一分鐘所得樣本予以抛棄，因爲其尚未充分粉碎。粉碎步驟剩下的8個樣本，使用N〇ble & w〇〇d手抄紙機分別形成8張手抄紙。 14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公愛） ί—私------.--訂---------線.，' (請先閱讀背面之注意事項再填寫本頁) 461929 A7 B7 五、發明說明（12 在檢驗及分析步驟中，紙共檢驗2 4張手抄紙，並以Μ/κ 形成試驗機分析。檢驗首先是目視，然後使用微形成試驗機及M/K系統公司之（絮凝/空隙）F1〇c/v〇id大小分析儀評估孩等手抄紙。微形成試驗機及（絮凝/空隙）F1〇c/v〇id分析儀測量紙張形成之下列四種性質：丨）形成指數-手抄紙均勻度之量度，指數愈高即等於均勻度愈佳，2)(絮凝）私數-、纟二測疋爲非纖維分離殘渣之手抄紙％，3 )平均絮凝大小指數-非纖維分離殘渣之大小，及4)絮凝強度指數_手抄紙絮凝部份與剩餘部份單位重量之差。手抄紙目視檢驗之結論是，使用上述條件時，全部樣本都可再製成漿。再者’以木質續酸㉝及木f續酸敏侧則即’樣本#2及#3)浸漬之襯紙板可再製成漿並形成較 /照但（亦即’樣本#1)更均勻之手抄紙。最後，全部指數都支持目视檢驗所觀察的—般傾向，亦即，由浸潰之襯紙板再製漿所形成的手抄紙與對照手抄紙—樣均勻或更均 2總言之，結論是，以所揭示木質續酸鹽及〖Μ麵組之木質纖維素材料，在未處理纖維素材料用以再製桌的相同溫和條件下，可再製成漿。 (請先閱讀背面之注意事項再填寫本頁) ^------,—訂---------絶經濟部智慧財產局員工消費合作社印製Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (11. Compared with a corrugated box made of lined cardboard treated with only lignosulfonate, the strength at 80% RH is increased by 100%. The final treated lignocellulosic material made from the combination of the disclosed lignosulfonate and κγΜΕΝΕ was also tested for repulpability and proved to be repulpable under mild conditions, as shown in the example below. Example 4 Repulpable The property test includes three steps. The first step is to pulverize the paper sample with a shredder, the second step is to form a handsheet from the pulverized sample, and the third step is to check and analyze the formed handsheet. In the study, two samples were evaluated: 1) control 35 # liner paper (Georgia_Pacitic's product USP70), 2) using MIPLY's pressurized saturation machine with calcium lignosulfonate (Georgia-pacitic's LIGN〇SITE 50; 22% added amount) impregnated 35 # liner board, and 3) made ffiMIpLY, s pressure saturated machine with calcium lignosulfonate (28 彳 added amount) and '0.2 mm direct control Mayer rod (about 1% added amount) after coating KYMENE 557LX Agent (produced by Hercules) 35 # liner board. In the pulverization step, the TAPPI / UK pulverizer (ΤΑρρι t_205) was run for 9 minutes, removing 125 ml of samples every minute. The pulverizer was equipped with a spiral baffle plate, a 3,000 rpm three-leaf propeller, and deionized water (pH = 74) at a temperature of 38C ± 6C (100 ° F to 10 ° F). The sample obtained in the pulverizing step is then formed into a handsheet in a forming step. The sample obtained in the first minute of the pulverization step was discarded because it was not sufficiently pulverized. The 8 samples remaining in the pulverization step were formed into 8 sheets of handsheets using a Noble & w00d handsheet machine, respectively. 14- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) ί—Private ------.-- Order --------- line., '(Please first Read the notes on the reverse side and fill out this page) 461929 A7 B7 V. Description of the invention (12 In the inspection and analysis steps, the paper inspects a total of 24 hand-made papers, and analyzes with a M / κ forming test machine. The inspection is first visually, Then use a micro-formation testing machine and M / K Systems' (flocculation / void) F10c / void size analyzer to evaluate children's handsheets. Micro-formation testing machine and (flocculation / void) F10c / v〇 The id analyzer measures the following four properties of paper formation: 丨) formation index-a measure of the uniformity of hand-made paper, the higher the index is, the better the uniformity is, 2) (flocculation) private number-the second test is non-fiber % Of hand-made paper for separation residue, 3) average flocculation size index-the size of non-fiber separation residue, and 4) flocculation strength index_the difference between the unit weight of the flocculated part of the hand-made paper and the remaining part. The visual inspection of handsheets concluded that all of the samples could be repulped using the above conditions. In addition, the 'wood-based acid and wood-based acid-sensitive sides are' samples # 2 and # 3) The impregnated lining paperboard can be repulped and formed more uniformly / photogenic (ie, 'sample # 1). Hands copy paper. Finally, all the indices support the general tendency observed by visual inspection, that is, the handsheet formed from the repulping of impregnated linerboard and the control handsheet are uniform or even 2 In summary, the conclusion is Based on the disclosed lignocellulose and the lignocellulosic material of the [M face group], the same mild conditions as the untreated cellulosic material used for remaking the table can be repulped. (Please read the notes on the back before filling out this page) ^ ------,-Order --------- printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

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Claims

4第88jl9f66號專利申請案口中今專利範圍修正本(9〇年4月） A8 B8 C8 D84 Patent Application No. 88jl9f66 Kou Zhongjin Amendment of Patent Scope (April 90) A8 B8 C8 D8

年月申請專利範圍Year and scope of patent application

經濟部中央標準局貝工消費合作社印製 1. 一種加至木質纖維素材料以改良該材料在潮濕條件下之強度的產物，該產物包含： a )具有至少一個項酸單元之水溶性強化劑；及 b )具有至少一個吖啶環之化合物。 2. 根據申請專利範圍第1項之產物，其中該水溶性強化劑係自木質付生物及其混合物所組成之族群中所選出。 '、 3 ·根據申請專利範圍第2項之產物，其中該木質衍生物係自木質磺酸之金屬鹽，木質磺酸之銨鹽及任何進一步化學改質木質磺酸化合物（其中保留親核磺酸單元），及其混合物所組成之族群中所選·出。、 4.根據申請專利範圍第丨项之產物，其中該具有至少一個吖啶環乏化合物係自聚醯胺_聚胺_表氯醇化合物孕其混合物所組成之族群中所選出。 5 · —種改良木質纖維素材料在潮濕情況下之強度的方法，該方法包含下列步騾： a) 將具有至少一個磺酸單元之水溶性強化劑施加於木質纖維素材料；及 b) 將具至少一個吖啶環之化合物施加於具該強化劑之木質纖維素材料。 6. 根據申請專利範圍第5項之方法，該水溶性強化劑係自木質衍生物及其混合物所組成之族群中所選出。 7. 根據申請專利範園第6項之方法，其中該木質衍生物係自木質磺酸之金屬鹽’木質磺酸之銨鹽，及任何進一步化學改質木質橫酸化合物（其中保留親核磺酸單元）， - -I - I m I HI 1—i ϊ - - .larR, 1^1. - Hi —I— 11 - I \i U9. ys (請先閲讀背面之注項再填寫本頁) --*Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 1. A product added to lignocellulosic material to improve the strength of the material under humid conditions, the product comprising: a) a water-soluble enhancer with at least one acid unit And b) a compound having at least one acridine ring. 2. The product according to item 1 of the patent application scope, wherein the water-soluble enhancer is selected from the group consisting of woody byproducts and mixtures thereof. ', 3. The product according to item 2 of the scope of the patent application, wherein the wood derivative is a metal salt of lignosulfonic acid, an ammonium salt of lignosulfonic acid, and any further chemically modified lignosulfonic acid compound (wherein the nucleophilic sulfonic acid is retained Acid units), and their mixtures. 4. The product according to item 1 of the scope of the patent application, wherein the compound having at least one acridine ring is selected from the group consisting of polyamidoamine_polyamine_epichlorohydrin compound and a mixture thereof. 5. A method for improving the strength of a lignocellulosic material under wet conditions, the method comprising the following steps: a) applying a water-soluble strengthening agent having at least one sulfonic acid unit to the lignocellulosic material; and b) applying A compound having at least one acridine ring is applied to the lignocellulosic material with the strengthening agent. 6. According to the method in claim 5 of the scope of patent application, the water-soluble enhancer is selected from the group consisting of wood derivatives and mixtures thereof. 7. The method according to item 6 of the patent application park, wherein the wood derivative is derived from the metal salt of lignosulfonic acid, the ammonium salt of lignosulfonic acid, and any further chemically modified lignosulfonic acid compounds (wherein the nucleophilic sulfonic acid is retained Acid unit),--I-I m I HI 1—i ϊ--.larR, 1 ^ 1.-Hi —I— 11-I \ i U9. Ys (Please read the note on the back before filling this page )-*

461929 A8 B8 C8 D8 申請專利範圍及其混合物所组成之族群中所選出。根，申請專利範圚第5項之方法，其中該具有至少—個，丫 9, - -I— In ....... --I I I ^^1 - 1 n ..... -- - I .(-¾. u-d (請先閲讀背面之注意事項再填寫本頁) 化合物係自聚醯胺-聚胺-表氯醇化合物及其混合物所組成之族群中所選出。 σ :、種改良木質纖維素材料在潮濕情況下之強度的方法，該方法包含下列步驟： a) 將具有至少一個吖啶環之化合物施加於木質纖維素材料；及 b) 將具至少—個親核磺酸單元之水溶性強化劑施加於具该具吖啶環化合物之木質纖維素材料。根據申清專利範圍第9項之方法，該水溶性強化劑係自木質知生物及其混合物所組成之族群中所選出。 11.根據申請專利範固第i 0項之方法，其中該木質衍生物係自木質磺酸之金屬鹽，木質磺酸之銨鹽，及任何進一步化學改質木質磺酸化合物（其中保留親核磺酸單元），及其混合物所組成之族群中所選出。 12·根據申請專利範圍第9項之方法，其中該具有至少一個吖啶環之化合物係自聚醯胺-聚胺_表氯醇化合物及其混合物所組成之族群中所選出。經濟部中央標隼局員工消費合作社印製 13'種改良木質纖維素材料在潮濕情況下之強度的方法，該方法包含下列步驟： a) 將具有至少一個吖啶環之化合物與具有至少一個親核續酸單元之水溶性強化劑混合；及 b) 將該丫咬環化合物與水溶性強化劑之混合物施加 2- 本紙張尺度適用中國國家標準（CNS〉A4说格（210X297公缝 ^61929 A8 B8 C8 D8 、申請專利範圍於木質纖维素材料。 Η根據申請專利範園第13項之方法，其中水溶性強化劑係自木質衍生物及其混合物所組成之族群中所選出。 A J據中請專利範圍第14项之方法，其中該木質衍生物係自木質續酸之金屬鹽，木質續酸之録鹽，及任何進一步化學改質木質續酸化合物（其中保留親核績酸單兀）’及其混合物所組成之族群中所選出。此根據中請專利範圍第13項之方法，其中該具至少κ ，環之化合物係自聚酸胺-聚胺-表氯醇化合物及其混合物所組成之族群中所選出。、 (請先聞讀背面之注項再填寫本頁) I I ii I- - -- · -----------k----:—ίτ------- 經濟部中央榡隼局員工消費合作社印製 -3 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）蝉CM 12 申請 Ί! 案 88119766 類别 (以上各襴由本局填註）461929 A8 B8 C8 D8 Selected from the group of patent applications and their mixtures. Root, the method of applying for the fifth item of the patent application, which has at least one, ah 9,--I-In ....... --III ^^ 1-1 n .....- -I. (-¾. Ud (Please read the notes on the back before filling out this page) The compounds are selected from the group consisting of polyamido-polyamine-epichlorohydrin compounds and mixtures thereof. Σ :, species A method for improving the strength of a lignocellulosic material under wet conditions, the method comprising the steps of: a) applying a compound having at least one acridine ring to the lignocellulosic material; and b) applying at least one nucleophilic sulfonic acid The water-soluble strengthening agent of the unit is applied to the lignocellulosic material having the acridine ring compound. According to the method of claim 9 in the scope of the patent application, the water-soluble enhancer is selected from the group consisting of wood-dwelling organisms and their mixtures. 11. The method according to claim i 0 of the patent application, wherein the wood derivative is a metal salt of lignosulfonic acid, an ammonium salt of lignosulfonic acid, and any further chemically modified lignosulfonic acid compound (wherein the nucleophile is retained Sulfonic acid units), and mixtures thereof. 12. The method according to item 9 of the application, wherein the compound having at least one acridine ring is selected from the group consisting of polyamido-polyamine-epichlorohydrin compounds and mixtures thereof. A method for printing 13 'improved strength of lignocellulosic materials under wet conditions by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, which includes the following steps: a) A compound having at least one acridine ring and at least one Mixing of water-soluble fortifiers of the nuclear acid unit; and b) applying the mixture of the yam ring compound and water-soluble fortifier 2- This paper is in accordance with Chinese national standard (CNS> A4) (210X297 common seam ^ 61929 A8) B8 C8 D8. The scope of patent application is lignocellulosic materials. Η According to the method in the patent application park No. 13, wherein the water-soluble enhancer is selected from the group consisting of wood derivatives and mixtures thereof. AJ According to The method of claim 14, wherein the wood derivative is a metal salt of lignin, a salt of lignin, and any further chemical modification of lignin (which retains a nucleophilic acid) 'And its mixtures are selected from the group. This is according to the method of claim 13 in which the compound having at least κ and ring is self-polymerized Selected from the group consisting of amine-polyamine-epichlorohydrin compounds and their mixtures. (Please read the notes on the back before filling out this page) II ii I----------- ---- k ----: — ίτ ------- Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs -3 This paper size applies to China National Standard (CNS) A4 (210X297 mm) Cicada CM 12 Application: Case No. 88119766 Category (The above cases are filled out by this Office)

C4 461929 中文說明書修正頁(90年4月） 11專利説明書蠤名稱中文英文姓名國籍用於改良木質纖維素材料在潮濕條件下之強度的泽物及古法 _____ PRODUCT AND METHOD FOR IMPROVING THE STRENGTH OF LIGNOCELLULOSTC： MATERIAL UNDER WTIMID CONDITIONS 發明創作> 住、居所姓名 (名稱） 1. 布烈爾艾利克斯歐文斯 2. 狄米翠斯伊安尼斯可利阿斯 3·鞍德魯朱利安溫克 1.3.均美國 2.希臘 1.美國俄亥俄州飛爾菲爾德市俱樂屋路32號Ε楝 2_美國俄亥俄州梅森市西達村路4683號 3.美國俄亥俄州懷俄明市希頓法利路450號美國造紙技術法人基金會裝· 訂經濟部智慧財產局員工消費合作社印製線三、申請人本紙張尺度通用國籍住、居所 (事務所j 代表人娃名美國美國密西根州卡拉馬祖市西密西根大學約翰·柏金國國家標準（CNS) Α4规格（210 X 297公楚） 461929 第88119766號專利中請案中文說明書修正頁(90年4月）紙 4, -4 1咳^^ 年月 8 ' Α" — 四、中文發明摘要（發明之名稱：用於改良木質纖維素材料立潮濕條件下之強度）的產物及方法木質纖維素材料之強度，係藉以含磺酸單元之水溶性強化劑處理該材料並藉該強化劑與含吖啶環之化合物反應而使該強化劑變成水溶性，而獲得改良。因此，在與濕手接觸或在潮濕情況下被接觸時，該強化劑自木質纖維素材料之滲出即得以實質減少或消除。 I ^^^1 --- —^1 —1-1 - . -- -!| ί,ί (請先閲讀背面之注意事項再填寫本頁各欄) 英文發明摘要（發明之名稱： PRODUCT AND METHOD FOR IMPROVING THE STRENGTH OF LIGNOCELLULOSIC MATERIAL UNDER HUMID CONDITIONS 訂經濟部智慧財產局員工消費合作社印製 The strength of lignocellulosic materials is improved by treating them with water-soluble strengthening agents containing sulfonic units, and rendering these agents water-insoluble by reacting them with compounds containing azetidinium rings. Thus, a substantial reduction or elimination of the bleeding of said strengthening agents from ihc lignocellulosic materials when touched with wet hands or contacted under humid conditions is achieved. 2- 本紙張尺度適用中國國家標準（ CNS ) A4規格（210X297公釐）線C4 461929 Chinese Manual Correction Page (April, 1990) 11 Patent Specification 蠤 Name Chinese English Name Nationality Zeolite and ancient method for improving the strength of lignocellulose materials under wet conditions __ PRODUCT AND METHOD FOR IMPROVING THE STRENGTH OF LIGNOCELLULOSTC: MATERIAL UNDER WTIMID CONDITIONS Invention > Name of Residence and Residence (Name) 1. Brewer Elix Owens 2. Dimitris Iannis Collias 3. Saddle Julian Wink 1.3. Both the United States 2. Greece 1. 32 Galleon Road, Feldfeld, Ohio, United States 2__ 4683 West Village Road, Mason, Ohio, USA 3. 450 Heaton Farley Road, Wyoming, Ohio, USA The United States Paper Technology Corporation Foundation installed and ordered the printing line for employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives. 3. The applicant's paper size is a common nationality residence and residence. John Perkins National Standard (CNS) Α4 Specification (210 X 297 Gongchu) 461929 No. 88119766 Proposal for the amendment to the Chinese manual (April 1990) Paper 4, -4 1 cough ^^ Year 8 'Α " — IV. Abstract of the Chinese invention (Name of the invention: used to improve the lignocellulose material in wet conditions) Product and method of strength) The strength of lignocellulose material is that the material is treated with a water-soluble strengthening agent containing a sulfonic acid unit and the strengthening agent becomes water-soluble by reacting the strengthening agent with a compound containing an acridine ring. Therefore, the improvement is obtained. Therefore, the exudation of the reinforcing agent from the lignocellulosic material can be substantially reduced or eliminated when it comes into contact with wet hands or in contact with wet conditions. I ^^^ 1 --- — ^ 1 — 1-1-.--! | Ί, ί (Please read the notes on the back before filling out the columns on this page) English Abstract of the Invention The strength of lignocellulosic materials is improved by treating them with water-soluble strengthening agents containing sulfonic u nits, and rendering these agents water-insoluble by reacting them with compounds containing azetidinium rings. Thus, a substantial reduction or elimination of the bleeding of said strengthening agents from ihc lignocellulosic materials when touched with wet hands or contacted under humidifying conditions is achieved. 2 -This paper size applies to China National Standard (CNS) A4 (210X297 mm) line

年月申請專利範圍Year and scope of patent application